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EP1749065A2 - Phyllosilicate mineral sous forme de nanopoudre - Google Patents

Phyllosilicate mineral sous forme de nanopoudre

Info

Publication number
EP1749065A2
EP1749065A2 EP05753650A EP05753650A EP1749065A2 EP 1749065 A2 EP1749065 A2 EP 1749065A2 EP 05753650 A EP05753650 A EP 05753650A EP 05753650 A EP05753650 A EP 05753650A EP 1749065 A2 EP1749065 A2 EP 1749065A2
Authority
EP
European Patent Office
Prior art keywords
layered silicate
natural
mineral
particles
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05753650A
Other languages
German (de)
English (en)
Other versions
EP1749065B1 (fr
Inventor
Matthias Schuhbauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nottenkamper Hans Guenter
Original Assignee
Nottenkamper Hans Guenter
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nottenkamper Hans Guenter filed Critical Nottenkamper Hans Guenter
Publication of EP1749065A2 publication Critical patent/EP1749065A2/fr
Application granted granted Critical
Publication of EP1749065B1 publication Critical patent/EP1749065B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention relates to the conditioning of naturally occurring layered silicates, in particular in the form of illicit raw materials with an illite content of more than 70% and pronounced fine contents.
  • Layered silicates have a particle fineness in the range ⁇ 2 ⁇ m (this value is characteristic for the grain fineness of clay minerals), whereby the actual particle fineness can range from clearer fine areas down to nanoscale depending on the shape of the particles.
  • layered silicates with technically interesting platelet structures a general distinction is made between two-layer (kaolinite) and three-layer silicates (smectite, lllite).
  • the three-layer silicates in particular offer distinctive particle fineness.
  • the types of the smectite group are generally used technically and commercially. For this group there are relatively high deposits with sufficient purity and well-developed fineness.
  • the typical swelling capacity of this special silicate structure is used for deagglomeration, i.e. the separation of the individual particles from each other, using chemical processes.
  • the lllite group essentially comprises the types of muscovite and mica used for technical and commercial purposes. Their rock-like form requires a regular crushing process, especially since they do not have the plastic character of clay mineral materials such as kaolinite and smectite.
  • nanoscale particles are theoretically possible due to the lower level (due to the weathering process during the formation), but practically from a commercial and industrial point of view on the procedural effort for the production of sufficiently large production quantities and the high degree of chemical influence rather not implementable.
  • the nanoscale is also limited to the thickness of the platelets, while the surface remains microscopic. Muscovite and mica are classified macroscopically when viewed mineralogically. Muscovite and mica of the illite group are usually direct weathering products of the parent rock. In contrast, the actual clays are relocated to secondary deposits. During this rearrangement, the fine clay sediments that form the prerequisite for nanoscale particles are formed through mechanical, hydrothermal and chemical processes.
  • the three-layer minerals such as smectite and lllit
  • the two-layer minerals e.g. Kaolinite.
  • practice therefore focuses on smectite raw materials, since these are available in quantitatively usable deposits with sufficient levels of purity.
  • correspondingly fine-tuned illite with higher degrees of purity is practically non-existent or only to a very limited extent.
  • the general literature on clay minerals thus focuses on smectitic material with regard to industrial use, especially in the high-tech sector and with regard to nanoscale products.
  • DE 29 50 248 C2 relates to the production of multicomponent masses with the aim of homogenizing several components into a usable mass.
  • This objective is not comparable to that of the present invention, since in the case of the invention, a single component which is as pure as possible is used and which is to be broken down into its primary components in a very fine manner.
  • the product according to this known proposal is heavily moistened so that a special processing technique can be used.
  • This processing technique uses known machines and equipment such as Impact mill and classifier.
  • the fineness of grinding is specified as 90 ⁇ m and the grinding process takes the form of a comminution process.
  • US 2002/45010 A1 relates to a special application focused on a synthetic material, especially the coating of surfaces.
  • the basic material has only a very extensive relationship to lllit.
  • the material base is hectorite as clay mineral material and the description indicates the availability of nanoparticulate materials, so that logically it also mentions lllite, which is not used in practice.
  • the material hectorite is to be assigned to another group, namely the group of smectites. This is a synthetically manufactured material that is also chemically specifically geared towards the exchange of Mg for Li, and therefore has no relation to a purely natural material.
  • EP 1 394 197 A1 relates to highly viscous molding compositions based on thermoplastic polymers from the group consisting of polyamides, polyesters, polyether esters, polyester amides or their mixtures and nanoscale fillers, ie fillers with an average particle size in the range of ⁇ , suitable for the extrusion blow molding process 1 ⁇ m.
  • the problem to be solved is to provide highly viscous molding compositions based on thermoplastic polymers which are easy to produce, are suitable for the extrusion blow molding process and additionally have sufficient strength at temperatures of 150-200 ° C.
  • thermoplastic polymers which contain (a) nanoscale fillers in an amount of 0.5-15% by weight and (b) fibrous fillers in amounts of 5-30% by weight.
  • the filler particles have dimensions in the nanometer range, ie with an average particle size of ⁇ 1 ⁇ m (untreated fillers).
  • Suitable nanoscale fillers for the production of the nanocomposites are substances which can be added at any stage of the production and which can be finely distributed in the nanometer range. These nanoscale fillers can be surface-treated but also untreated fillers.
  • the fillers are preferably minerals that already have a layer structure, such as layer silicates, double hydroxides or graphite.
  • the nanoscale fillers used here are selected from the group of oxides, oxide hydrates of metals or semimetals, in particular from the group of oxides or oxide hydrates of an element selected from the group consisting of boron, aluminum, calcium, gallium, indium, silicon, germanium, tin , Titanium, zirconium, zinc, yttrium or iron.
  • the nanoscale fillers are either silicon dioxide or silicon dioxide hydrates.
  • nanoscale fillers in the polyamide molding compound are present as a uniformly dispersed layered material.
  • Preferred minerals are with a layered structure Layered silicates, double hydroxides, such as hydrotalcite or graphite, as well as nanofillers based on silicones, silicas or silsesquioxanes.
  • the nanoscale is repeatedly stated in a size range of on average ⁇ 1 ⁇ m.
  • the material according to the invention is specified with above average ⁇ 300 nm (0.3 ⁇ m) or with D50 ⁇ 150 nm (0.15 ⁇ m). That With regard to the nanoscale, the material according to the invention stands out from the prior art with regard to natural mineral layered silicates by almost a power of ten.
  • a sought-after mineral material with a layer structure had to essentially meet the following requirements and properties: a) the suitability for producing a nanoproduct, b) the achievement of an end product on the basis of a natural raw material , c) the property of a layered silicate with a three-layer structure that primarily has no or at most a low swellability, d) complete deagglomeration in the manufacture of the product, e) processability and conditioning without thermal pretreatment, f) processing without the use of chemical or synthetic processes.
  • lllite of the selected type unusually pure and extremely finely formed lllite (hereinafter referred to as "lllite of the selected type"), which meets the above-mentioned objectives or properties of the has a high degree of sought-after material and offers the possibility of directly converting the material into nanopowder by processing and conditioning steps according to the invention.
  • lllit is characterized by its special particle fineness down to the colloidal area as a raw material that is particularly suitable for the product objective according to the invention.
  • lllite is generally not fully developed to form colloidal layered silicate and is usually not of high purity, the objective has not been set up so far and has not been implemented.
  • smectic material e.g. Montmorillonite and bentonite.
  • Such a material is processed under thermal pretreatment, which results in the elasticity of the platelet structures due to crystal water losses.
  • This is particularly disadvantageous for sensitive use in the field of technical ceramics, but also for the swellability. No or no complete deagglomeration is achieved, but an "exfoliation" in the process of the user is required with the help of essential chemical additives and the use of swellability, i.e. the success of the application is on the customer's side and special process technologies and additional energy are required.
  • deagglomeration of the aggregated layered silicate particles is of crucial importance, the original composition of the material having to be preserved both chemically and mineralogically, primarily the process being carried out dry, in principle a wet process should not be ruled out, the layered silicate particles should not be crushed (in the sense of destruction), due to the deagglomeration of the sight crystals, it has no significant influence on the shape and structure of the material chemical and thermal treatments are avoided and no addition or removal of substances to and from the material takes place.
  • the starting product of the illitic raw material of the selected type is mechanically "pre-broken" in a deagglomeration device (while maintaining its mineral structure).
  • a deagglomeration device while maintaining its mineral structure.
  • the large agglomerates are greatly accelerated and swirled with large air masses.
  • the agglomerates are encountered when they meet and when they meet Impact surfaces separated from one another to such an extent that essentially primary crystallites are present, the product being deagglomerated by conditioning and the predominant amount of primary particles being approximately ⁇ 300 nm.
  • the deagglomerated layered silicate particles are removed as the desired product, thereby damaging them This crystallite is avoided.
  • the incompletely deagglomerated particles are returned as coarse material to the deagglomeration process
  • the output of the fine product increases the degree of deagglomeration. This can be optimized by various types of installations in the deagglomeration units in order to achieve a longer dwell time or a higher impact effect.
  • the starting material is pre-broken using conventional machines, for example roll crushers.
  • High-performance air classifiers with special classifying wheels adapted to this material are used for fine classifying.
  • Preparation machines that impact the agglomerates are used for the deagglomeration process.
  • Processing machines of this type can be impact mills, air jet mills, pin mills or ball mills.
  • special face plate mills for example clay digestion mills according to the Eirich system, with toothed grinding tracks has proven to be particularly advantageous in terms of performance and result.
  • the multitude of gaps between the grinding process form fine chambers for swirling at the prevailing high speeds and - based on the special feed material - result in a high impact effect.
  • the impact effect and the dwell time can be further improved by different mechanical installations.
  • an absolute nanopowder can be produced as a direct product.
  • a nanopowder which is produced in a completely unusual way and is based on the illite of the selected type, is already correspondingly nanoscale de-agglomerated in the product state, so that it is particularly good and with high proportions e.g. can be dispersed in polymer systems. Practical experience shows that the process costs are significantly lower and that significantly better property values (compared to nanoclays) are achieved.
  • the typical swellability of Smectite is used in nanoclays to chemically expand them and to exfoliate them in the process of the customer who is processing them.
  • the non-swellable illites of the selected type have the advantage that they do not experience any corresponding volume changes at corresponding voltages, which is a decisive advantage, particularly in ceramics.
  • the product produced according to the invention is distinguished by the fact that it is a purely mineral, natural, finely conditioned layered silicate, has a three-layer crystal structure, is essentially non-swellable and contains the mineral lllite with a proportion of more than 70% as the main component. the remaining fractions are pronounced fine fractions, have a solid powdery state of aggregation and a particle diameter of ⁇ 300 nm and are reactive with regard to ion exchange and charge. Furthermore, this material obtained with the invention has, for use in practice, essential intrinsic properties of free-flowing and free-flowing properties, largely no tendency to agglomerate and a lack of hygroscopic tendency, high wettability, and is therefore homogenizable and safe to use.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne la production d'un produit minéral à base de phyllosilicate d'aluminium et de fines particules correspondantes, avec une proportion de l'ordre de 70 % du minéral illite du type sélectionné. Selon l'invention, le matériau de départ est préconcassé dans sa composition naturelle, les particules de phyllosilicate agglutinées sont soumises à une désagglomération, sous accélération élevée, et sont mises à tourbillonner, sous l'effet de masses d'air importantes. Les agglomérats sont désintégrés par impact mutuel et contre des surfaces d'impact, jusqu'à obtention de cristallites primaires. Les particules de phyllosilicate désagglomérées sont extraites par criblage fin et les particules désagglomérées sont réintroduites dans le circuit et les cristallites primaires sont désagglomérés.
EP05753650A 2004-05-14 2005-05-13 Phyllosilicate mineral sous forme de nanopoudre Expired - Lifetime EP1749065B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004023992 2004-05-14
PCT/DE2005/000883 WO2005111154A2 (fr) 2004-05-14 2005-05-13 Phyllosilicate mineral sous forme de nanopoudre

Publications (2)

Publication Number Publication Date
EP1749065A2 true EP1749065A2 (fr) 2007-02-07
EP1749065B1 EP1749065B1 (fr) 2008-10-29

Family

ID=35311133

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05753650A Expired - Lifetime EP1749065B1 (fr) 2004-05-14 2005-05-13 Phyllosilicate mineral sous forme de nanopoudre

Country Status (6)

Country Link
US (1) US7571869B2 (fr)
EP (1) EP1749065B1 (fr)
AT (1) ATE412711T1 (fr)
DE (1) DE502005005818D1 (fr)
ES (1) ES2317252T3 (fr)
WO (1) WO2005111154A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010007820A1 (de) 2010-02-11 2011-08-11 Granulat GmbH, 53842 Selbstverlöschendes Extrudat aus einer thermoplastischen Polyurethanzusammensetzung und Verfahren zu dessen Herstellung
ES2364211B1 (es) * 2010-02-16 2012-08-10 Nanobiomatters Industries, S.L. Procedimiento de obtención de partículas de filosilicatos laminares con tamaño controlado y productos obtenidos por dicho proceso.
CN108516562A (zh) * 2018-06-07 2018-09-11 苏州中材非金属矿工业设计研究院有限公司 一种凹凸棒石粘土的提纯工艺
CN109053170A (zh) * 2018-08-23 2018-12-21 广西皇宝瓷业有限公司 一种纳米氧化镁陶瓷及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041238A (en) * 1958-08-06 1962-06-26 Minerals & Chem Philipp Corp Method of preparing activated attapulgite
US3951850A (en) * 1973-06-22 1976-04-20 Clocker Edwin T Conversion of clay to its colloidal form by hydrodynamic attrition
DE2950248A1 (de) * 1978-12-13 1980-06-26 Netzsch Maschinenfabrik Verfahren und vorrichtung zum aufbereiten von versatzstoffen zu keramischen massen, glasuren oder fritten
JPS5879810A (ja) * 1981-10-30 1983-05-13 Kunimine Kogyo Kk ベントナイトの改質方法
US5934575A (en) * 1996-12-27 1999-08-10 Canon Kabushiki Kaisha Pneumatic impact pulverizer and process for producing toner
AR032424A1 (es) * 2001-01-30 2003-11-05 Procter & Gamble Composiciones de recubrimiento para modificar superficies.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005111154A3 *

Also Published As

Publication number Publication date
ATE412711T1 (de) 2008-11-15
ES2317252T3 (es) 2009-04-16
EP1749065B1 (fr) 2008-10-29
US7571869B2 (en) 2009-08-11
US20070227403A1 (en) 2007-10-04
WO2005111154A2 (fr) 2005-11-24
WO2005111154A3 (fr) 2007-03-22
DE502005005818D1 (de) 2008-12-11

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